Substituted chrysanthemumates

ABSTRACT

New and valuable chrysanthemumates, particularly esters having triunsaturated alcohols, and a process for controlling pests with these esters.

United States Patent Vollrath et al.

3,673,215 [451 June 27, '1972 SUBSTITUTED CHRYSANTHEMUMATES Inventors: Robert Vollrath, Bad Duerkheim; Axel Nuerrenbach, Gruenstadt; Heinrich Adolphi, Limburgerhof, all of Germany Assignee: Badische Anilin -& Soda-Fabrik Aktiengeselischaft, Ludwigshafen/ Rhine, Land Rhineland and- Pfalz, Germany Filed: Aug. 14, 1969 Appl. No.: 850,242

Foreign Application Priority Data Aug. 29, 1968 Germany ..P 17 93 312.9

us. Cl. ..260/332.2 R, 260/3323 R, 260/340.5, 260/347.4, 260/347.8, 260/468 P, 260/618,

int. 0 ..C07d 63 12, C07C 69/74, A611: 27/00 [58] Field of Search ..260/332.2 R, 340.5, 347.4,

Primary Examiner-Henry R. Jiles Assistant Examiner-Cecilia M. Shurto Attorney-Johnston, Root, OKeeffe, Keil, Thompson & Shurtleff [5 7] ABSTRACT New and valuable chrysanthemumates, particularly esters having triunsaturated alcohols, and a process for controlling pests with these esters.

10 Claims, No Drawings SUBSTITUTED CEHIYSANTEEMUMATES The invention relates to new and valuable chrysanthemumates, especially esters having triunsaturated alcohols, and to pesticides containing them.

It is known to use various substituted benzyl esters of chrysanthemurnic acid as insecticides (US. Pat. Nos. 2,857,309; 3,358,011); further, some chrysanthemumates of alkylynols are known which have herbicidal properties (US. Pat. No. 3,285,950). However, their action is not completely satisfactory.

We have now found that chrysanthemumates having the formula where X denotes a phenyl group having the formula R, R R and R each denoting hydrogen, halogen (chlorine, bromine, iodine, fluorine), an alkyl radical having one to three carbon atoms, trihalomethyl (fluorine, chlorine, bromine, iodine), the radicals R to R being identical or different, R denoting hydrogen, halogen (chlorine, bromine, iodine, fluorine), trihalomethyl (chlorine, bromine, iodine, fluorine), an alkyl radical having one to three carbon atoms, an alkenyl radical having two to three carbon atoms, R and R together denoting the radical CH- CHCH CH, R and R together denoting the methylenedioxy radical, or X denotes a heteroaromatic radical having the formula where Y denotes oxygen or sulfur and R denotes hydrogen, an alkyl radical having one to three carbon atoms or a benzyl radical, are eminently suitable for controlling pests and are distinguished by a good insecticidal action on houseflies and cockroaches. Their action is superior to that of the abovementioned prior art active ingredients.

The compounds according to the invention may be easily produced, e.g. by reaction of a correspondingly substituted a1- dehyde with acetylene to give prop-2-ynol in accordance with the formula and esterification of the prop-2-ynol with chrysanthemurnic acid derivatives in accordance with the formula X having the meanings given above and Z denoting, for example, halogen (chlorine).

The prop2-ynols are preferably prepared from the aldehydes with sodium acetylide in tetrahydrofuran as solvent at temperatures of from 0 to 60 C, preferably room temperature.

The following solvents may also be used instead of tetrahydrofuran: benzene, toluene, ether, dioxane, at from 0 to 60 C, and liquid ammonia at 30 C. Reaction times are two to 12 hours depending on the type and number of substituents, the reaction temperature and the type of solvent.

The best results are obtained when the compounds according to the invention are produced by reaction of the prop-2- ynols with chrysanthemurnic acid chloride in an inert organic solvent, e. g. benzene, toluene, ligroin, ether, tetrahydrofuran or chloroform in the presence of an inorganic or organic base, e. g. sodium hydroxide, triethylamine or pyridine at temperatures of from 0 to 60 C. Reaction times are one to eight hours, depending on the type of substituents and the reaction temperature.

The production of the compounds according to the invention is illustrated by the following: i a. Preparation of l-(m-toluyl)-prop-2-ynol 12 parts by weight of rn-toluylaldehyde dissolved in 15 parts of tetrahydrofuran is dripped, while stirring and at 20 C, into a suspension of 24 parts of sodium acetylide in 150 parts of tetrahydrofuran; the whole is stirred for six hours at room temperature. The reaction mixture is decomposed with 100 parts of saturated ammonium chloride solution while cooling with ice; the organic phase is separated, washed with saturated sodium chloride solution and dried over sodium sulfate. After the tetrahydrofuran has been distilled off, the crude product is purified by fractional distillation.

Compound b.p. ("C/mm) l-phenylprop-2-ynol 60 l 0. l l-(p-chl0r0phenyl)-prop-2-ynol to 0.2 l-( m-chlorophenyl)-prop-2-ynol 85 0.3 l-(2',4' -dichl0rophcnyl) prop-2=-ynol (m.p. 53 to 54) l-(3,4' -dichlorophenyl)-prop-2-ynol 0.05 l-(m-fluorophenyl)-prop-2-ynol 59 to 65 0.1 l-(m-bromophenyl)-prop2-ynol ll4 1.5 l-(m-toluyl)'prop-2-ynol 71 to 73 0.1 1-(p-toluy1)-prop-2-yno1 72 to 75 0.1 l-(m-trifluoromethylphenyl)-prop-2-ynol 108 to l4 1-(2',4' -dimethylphenyl)-prop-2-ynol 93 to 97 0.25 l-(3',4' -dirnethylphenyl)-prop-2-ynol 85 to 88 0.1 l-(p-isopropylphenyl)-prop-2-ynol 92 to 93 l 0.2 l-(p-allylphenyl)-prop-2-ynol 86 to 91 0.1 l-(B-naphthyU-prop-Z-ynol (m.p. 60 to 64) l-(2' furyl)-prop-2-ynol 54 to 59 0.15 l-(2' -methyl-4' -furyl)-prop-2-ynol 115 to 20 1-(2' -benzyl-4' -furyl)-prop-2-ynol 128 to 0.1 l-(2' -methyl-5' -furyl)-prop-2-ynol 90 to 99 l4 l-(2' -thienyl)-prop-2-ynol 74 0.2 l-(3',4' -methylendioxyphenyl)-prop-2- ynol 113to1l6 [0.15 l-(2' -bromo-3',4' -methylendioxyphenyl prop-2-yno1 (m.p. 101 to 103) b. Preparation of chrysanthemumate 18.8 parts by weight of chrysanthemurnic acid chloride is dripped, while stirring and cooling with ice, into 14.6 parts of l-(m-toluyl)-prop-2-ynol and 16 parts of dry pyridine or triethylamine in dry benzene, toluene or ether. The reaction mixture is subsequently stirred for several hours at room temperature or for one hour at 40' to 60 C. After water has been added, the organic phase is separated, washed with dilute sulfunc acid, sodium bicarbonate and water, dried and concentrated. The crude chrysanthemumate is purified by vacuum distillation or by chromatography with aluminum oxide.

The pesticides according to this invention may be used as solutions, emulsions, suspensions or dusts. The form of application depends entirely on the purpose for which the agents are being used; in any case it should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, hydrocarbons, such as tetrahydronaphthalene, and alkylated naphthalenes are suitable.

Aqueous formulations may be prepared from emulsion conwith water may be prepared from active ingredient, emulsifying or dispersing agent and possibly solvent.

' Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier.

centrates, pastes or wettable powders by adding water. To 5 Th f u prepare emulsions the ingredients as such or dissolved in a sole 9 owing coniparanve expenme. demonsuine the ivent may be homogenized in water by means of wetting or P 9 action f h comPosmons according to this dispersing agents. Concentrates which are suitable for dilution mvemlon over known acuve mgredlems' R /C=CH\ (I) E C H H3O CHCH-C-OCH- CH3 CH3 Active ingredient number B.p. O./mm.) Analysis 1 R Q 133 to 138/0.1 C, 80.5 (80.9); H, 8.0 (7.8)

R-CI 01, 11.5 11.2).

3 Cl 111 to 11B/0.01 C, 71.8 (72); H. 6.8 (6 6),

4 Cl C, 64 7 (65.1); H, 5.9 (5.7),

R Cl

5 C1 C, 65.4 (65.1); H, 6.1 (5.7);

I 61, 20.1 21.0). R \"Cl 6 I; 111 to 112/0. 05 C, 75.8 (76.0); H, 7.2 (7.0).

7 Br C,63.0 (63.2);H,61(58),

I Br, 21 s 22.1

s n 120 to 13010.2 0,611.0 (68.6); H, 6.2 (6.0).

9 R Q CH C, 81.1 (81.1); H, 8.4 (8.1)-

11 CIJH C, 81.2 (81.4); H, 8.7 (8.3).

12 CH C, 81.5 (81.2); H, 8.7 (8.3).

13 CH3 C, 81.2 (81.5); H, 8.8 (8.7).

R CH2 CH=CHz 818 (82 0), H, 8.4 (8.1).

EXA P E 1 Active ingredient amount (pans by weight) of the active ingredient in the water 1 mm of acetonic solution of the active ingredients was pipetted onto the abdomen of houseflies (Musca domestica). 5 5 Q01 ppm effective After four hours mortality counts were made for the different F 1 ppm fl ti concentrations and the LD values calculated from them. G 0.04 ppm effective H 0.02 ppm effective A to E m ineffective Active ingredient LD in 'y/fly pp 1O 1 L25 EXAMPLE 4 2 0.18 3 0.1 1 Action on Caterpillars of the Cabbage Moth (Plutella 4 036 maculipennis) 5 0.083 I 6 025 Cabbage leaves were dipped into an aqueous emulsion of 3 352 the active ingredients. After the coatings had dried, caterpil- 9 lars of the cabbage moth were placed on the leaves. After 48 i0 0.l5 hours the kill rate was determined and the damage caused by 1 l the caterpillais assessed. l2 0.24 13 0.3 5 Q15 Active ingredient content by weight) 17 0.37 of the active ingredient 18 0.1 in the emulsion 0,4 0.4 i? 13 2 5 2 0.0] effective A 2 I 5 0.02 effective H 2 2| 0.02 effective C 2 22 0.05 efi'ective D 2 A. C. D. E 0.1 ineffective E 2 B 0.1 effective F O 1 effective EXAMPLE 2 These experiments clearly reveal the superiority of the new' compounds according to the invention over prior art active in- Sustained Exposure of Oriental Cockroach (Blatta orientalis) gredlems' We claim: Acetonic solutions of the active ingredients were evenly dis- A chrysanthemumate having the formula tributed in 1 liter beakers. After the solvent had evaporated, adult cockroaches were placed in the beakers and the action CHa cert daft 48h .A was as ame er ours concentration killing 80 H C O C O I C E C H 100 percent of the animals was designated effective.

CH; C X Active ingredient amount of active ingredient C H3 in mg/beaker I 2 25 v efiective where X denotes a phenyl group having the formula 4 2.5 effective 5 2.5 efiective q 9 2.5 efiective f l0 1 effective 1 1 0.5 effective -R 12 2.5 effective I I 13 2.5 effective 14 2.5 effective R5 R4 15 2.5 effective 16 2.5 effective L7; 2.5 effective R, R R and R each denoting hydrogen, halogen, an alkyl effective radical having one to three carbon atoms, trihalomethyl, the 21 1 effective 1 4 3 A 10 i fi' i radicals R to R being identical or different, R denoting B 10 ineffective hydrogen, halogen, trihalomethyl, an alkyl radical having one 3 :3 fnefieclive to. three carbon atoms, an alkenyl radical having two to three E 10 5:22:23 carbon atoms, R and R together denoting the radical CH F 5 ff ti Cl-l-CH CH--, R and R together denoting the G 5 effective methylenedioxy radical, said phenyl group having at most two of said radicals and the remaining of R through R being hydrogen, or X denotes a heteroaromatic radical having the EXAMPLE 3 fmmula Action on Mosquito Larvae (Aedes aegypti) JI Y Larvae of the mosquito (Aedes aegypti) in the fourth larval stage were introduced into 200 ml vessels holding water. An where Y denotes oxygen or sulfur and R denotes hydrogem, aqueous formulation of the active ingredients was then added an alkyl radical having one to three carbon atoms or u hcnzyl and the action was ascertained after 24 hours. Mortalities of radical. more than 80 percent were designated effective. 2. A chrysanthemumate as claimed in claim 1 wherein X denotes chlorophenyl.

denotes tolyl.

8. A chrysanthemumate as claimed in claim 1 wherein X denotes furyl.

9. A chrysanthemumate as claimed in claim 1 wherein X denotes thienyl.

10. A chrysanthemumate as claimed in claim 1 wherein X denotes naphthyl. 

2. A chrysanthemumate as claimed in claim 1 wherein X denotes chlorophenyl.
 3. A chrysanthemumate as claimed in claim 1 wherein X denotes dichlorophenyl.
 4. A chrysanthemumate as claimed in claim 1 wherein X denotes bromophenyl.
 5. A chrysanthemumate as claimed in claim 1 wherein X denotes trifluoromethylphenyl.
 6. A chrysanthemumate as claimed in claim 1 wherein X denotes 3'',4'' -methylenedioxyphenyl.
 7. A chrysanthemumate as claimed in claim 1 wherein X denotes tolyl.
 8. A chrysanthemumate as claimed in claim 1 wherein X denotes furyl.
 9. A chrysanthemumate as claimed in claim 1 wherein X denotes thienyl.
 10. A chrysanthemumate as claimed in claim 1 wherein X denotes naphthyl. 